JP7491284B2 - Hydrophilic water-slipping agent, laminate, and method for forming a film of hydrophilic water-slipping agent - Google Patents

Description

This disclosure relates to a hydrophilic water-slipping treatment agent, a laminate having a coating of the hydrophilic water-slipping treatment agent, and a method for forming a coating of the hydrophilic water-slipping treatment agent.

When water droplets remain on the surface of an item for a certain period of time, undesirable phenomena occur in terms of the appearance, function, or hygiene of the surface of the item. For example, if a car is left under sunlight with water droplets on it, the water droplets act as lenses, resulting in stains on the car body. In heat exchangers, in order to increase the surface area as much as possible from the viewpoint of improving exchange efficiency, multiple fins are arranged at close intervals, so that water generated by condensation may bridge between the fin materials, increasing ventilation resistance, reducing heat exchange efficiency, generating noise, and causing problems such as contamination due to scattering of water droplets. In addition, if water droplets are left on the surface of an item, mold may grow. Furthermore, if the environment in which the item is placed is low temperature, the water droplets may freeze and impair the appearance and function of the item. In particular, in heat exchangers used in outdoor units in cold regions, if the water generated by condensation freezes, ventilation resistance increases significantly. In order to reduce ventilation resistance, it is necessary to melt the frozen ice, which requires energy that is not directly related to heat exchange, resulting in a problem of high costs. Known solutions to these problems include methods of making the surface of an article water-repellent or hydrophilic (Patent Documents 1 and 2).

Japanese Patent Application Laid-Open No. 09-118875 Japanese Patent Application Laid-Open No. 06-322292

However, when water adheres to an article whose surface has been treated to be water repellent as in Patent Document 1, the contact angle of the water with respect to the surface of the article becomes large, and the water often remains on the surface of the article as a large number of small droplets, which can cause the remaining droplets to freeze or develop mold. On the other hand, when water adheres to an article whose surface has been treated to be hydrophilic as in Patent Document 2, the more hydrophilic the water is, the more the water spreads and stabilizes on the substrate, making it more difficult to remove. Although this promotes the evaporation of water, there is a problem that the water freezes or develops mold before it evaporates.

The problem to be solved by this disclosure is to provide a hydrophilic water-slipping treatment agent, a laminate having a film of the hydrophilic water-slipping treatment agent, and a method for forming a film of the hydrophilic water-slipping treatment agent. When water droplets or water generated by condensation adhere to a hydrophilic water-slipping film, the water tends to spread due to the hydrophilicity, promoting the formation of water droplets of a certain size or larger on the surface of the article, and when the water reaches a certain weight or more, the water droplets slide on the water-slipping film and are removed from the hydrophilic water-slipping film.

After extensive research, the inventors discovered that the above problems can be solved by using a specific hydrophilic water-slippery treatment agent.

The present disclosure provides the following:
(Item 1)
A polymer (A) containing a radical polymerizable monomer having a carboxy group and/or a salt thereof (a-1) as a reaction component;
and hydroxyethyl cellulose (B),
a mass ratio of the component (A) to the component (B) [(A)/(B)] in terms of solid contents is 5/95 to 95/5;
A hydrophilic, water-slipping treatment agent having a pH of 2.0 to 5.0 in an aqueous solution containing the combined solids concentration of components (A) and (B) of 1%.
(Item 2)
2. The hydrophilic, water-slipping treatment agent according to item 1, wherein the viscosity (mPa·s/25° C.) of component (B) at a solids concentration of 2% is 1 to 600.
(Item 3)
3. The hydrophilic smoothing treatment agent according to item 1 or 2, wherein the component (a-1) contains at least one member selected from the group consisting of (meth)acrylic acid, salts of (meth)acrylic acid, itaconic acid, salts of itaconic acid, itaconic acid monoesters, salts of itaconic acid monoesters, and itaconic anhydride.
(Item 4)
4. The hydrophilic smoothing treatment agent according to any one of items 1 to 3, wherein the component (a-1) accounts for 29 mol % or more of the monomers constituting the polymer of the component (A).
(Item 5)
5. The hydrophilic water-slipping treatment agent according to any one of items 1 to 4, wherein the component (A) is at least one selected from the group consisting of poly(meth)acrylic acid, a copolymer of (meth)acrylic acid and (meth)acrylamide, a copolymer of (meth)acrylic acid and an anionic monomer other than (meth)acrylic acid, a copolymer of (meth)acrylic acid, (meth)acrylamide and an anionic monomer other than (meth)acrylic acid, and salts thereof.
(Item 6)
6. A laminate having a coating of the hydrophilic water-slipping treatment agent according to any one of items 1 to 5 on at least one surface of a substrate.
(Item 7)
6. A method for forming a coating of a hydrophilic water-slipping treatment agent, comprising a step of applying the hydrophilic water-slipping treatment agent according to any one of items 1 to 5 to a surface of a substrate.

The hydrophilic water-slipping treatment agent provided in this disclosure improves the hydrophilic water-slip properties of the surface of a substrate or article when a film is formed on the surface of the article.

Throughout this disclosure, the range of the values of the physical properties, contents, etc. may be set as appropriate (for example, by selecting from the upper and lower limit values described in each item below). Specifically, for the value α, if the lower limit of the value α is exemplified as A1, A2, A3, etc. and the upper limit of the value α is exemplified as B1, B2, B3, etc., the range of the value α is exemplified as A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. In addition, in this disclosure, "to" is used to mean that the values described before and after it are included as the lower limit and upper limit.

<Component (A)>
The component (A) is a polymer containing a radically polymerizable monomer having a carboxy group and/or a salt thereof (a-1) (also referred to as "component (a-1)" in the present disclosure) as a reaction component. The radically polymerizable monomer refers to a monomer having a radically polymerizable functional group. Examples of the radically polymerizable functional group include a group having a carbon-carbon double bond and a group having a carbon-carbon triple bond. Specific examples of the radically polymerizable functional group include a (meth)acryloyl group and a vinyl group.

Examples of monomers constituting the polymer of component (A) include anionic monomers, cationic monomers, and nonionic monomers. Examples of anionic monomers include a radical polymerizable monomer having a carboxy group and/or a salt thereof (a-1), a radical polymerizable monomer having a sulfonic acid group (sulfo group) and/or a salt thereof (a-2) (also referred to as "component (a-2)" in this disclosure), a radical polymerizable monomer having a phosphoric acid group and/or a salt thereof (a-3) (also referred to as "component (a-3)" in this disclosure), and the like. Examples of cationic monomers include a radical polymerizable monomer having an amino group and/or a salt thereof (a-4) (also referred to as "component (a-4)" in this disclosure), and the like. Examples of nonionic monomers include radical polymerizable monomers (a-5) having a hydroxyl group (also referred to as "component (a-5)" in this disclosure), radical polymerizable monomers (a-6) having an amide group (also referred to as "component (a-6)" in this disclosure), radical polymerizable monomers (a-7) having an ester bond (also referred to as "component (a-7)" in this disclosure), and radical polymerizable monomers (a-8) having a nitrile group (also referred to as "component (a-8)" in this disclosure). In this disclosure, anionic monomers and cationic monomers refer to monomers that are negatively ionized when dissolved in water and ionized, and monomers that are positively charged are referred to as cationic monomers. In this disclosure, nonionic monomers refer to monomers that are not ionized when dissolved in water.

By including the (a-1) component as a monomer constituting the polymer of the (A) component, a film with good hydrophilic water sliding properties can be formed. Examples of the (a-1) component include a radical polymerizable monomer having one carboxy group, a radical polymerizable monomer having two carboxy groups, an anhydride of a radical polymerizable monomer having two carboxy groups, a monoester of a radical polymerizable monomer having two carboxy groups, a salt of the above monomer, and a salt of a monoester of the above monomer. Examples of radical polymerizable monomers having one carboxy group include (meth)acrylic acid, carboxyethyl (meth)acrylate, 2-(trifluoromethyl)(meth)acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid. Examples of radical polymerizable monomers having two carboxy groups include maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloromaleic acid. Examples of anhydrides of radical polymerizable monomers having two carboxy groups include maleic anhydride, itaconic anhydride, citraconic anhydride, and chloromaleic anhydride. Examples of monoesters of radical polymerizable monomers having two carboxy groups include maleic acid monoesters (e.g., monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.), fumaric acid monoesters (e.g., monomethyl fumarate, monoethyl fumarate, etc.), and itaconic acid monoesters (e.g., monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.). Examples of salts of the present disclosure include metal salts, onium salts (e.g., ammonium salts, phosphonium salts, etc.). Examples of metal salts of the present disclosure include alkali metal salts (e.g., lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (e.g., magnesium salts, calcium salts, etc.), etc. In the present disclosure, the term "salt" is not limited to salts formed by all of the functional groups (e.g., carboxy groups, etc.) in the component, but may also include salts formed by some of the functional groups contained in the component. Component (a-1) is preferably at least one selected from the group consisting of (meth)acrylic acid, salts of (meth)acrylic acid, itaconic acid, salts of itaconic acid, itaconic acid monoesters, salts of itaconic acid monoesters, and itaconic acid anhydride, because it can exhibit good hydrophilic water sliding properties, especially when used in combination with component (B).

Examples of component (a-2) include sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-allyloxy-2-hydroxy-1-propanesulfonic acid, methallyl sulfonic acid, 3-((meth)acryloyloxy)propanesulfonic acid, and salts of the above monomers. Of the components (a-2), methallyl sulfonic acid is preferred because it can be used as a chain transfer agent and is easy to control the viscosity.

Examples of component (a-3) include vinylphosphonic acid, 2-(meth)acryloyloxyethyl acid phosphate, and salts of the above monomers.

Examples of the (a-4) component include 2-(dimethylamino)ethyl (meth)acrylate hydrochloride, 2-aminoethyl (meth)acrylate hydrochloride, N-(3-aminopropyl) (meth)acrylate hydrochloride, [3-((meth)acryloylamino)propyl]trimethylammonium chloride, [2-((meth)acryloyloxy)ethyl]trimethylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, 2-aminoethyl(meth)acrylamide hydrochloride, N-(3-aminopropyl)-(meth)acrylamide hydrochloride, diallyldimethylammonium chloride, allylamine hydrochloride, vinylimidazolium hydrochloride, vinylpyridinium hydrochloride, vinylbenzyltrimethylammonium chloride, 2-((meth)acryloyloxy)ethyltrimethylammonium methylsulfate, and 3-((meth)acrylamido)propyltrimethylammonium methylsulfate.

Examples of component (a-5) include vinyl alcohol, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

Examples of the (a-6) component include (meth)acrylamide, vinylacetamide, N-methoxymethyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-t-butyl(meth)acrylamide, N-t-octyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N'-methylenebis(meth)acrylamide, and 1,3,5-triacryloylhexahydro-1,3,5-triazine. Among the (a-6) components, N,N'-methylenebis(meth)acrylamide and/or 1,3,5-triacryloylhexahydro-1,3,5-triazine are preferred because they can be used as crosslinkable polyfunctional monomers and are easy to control the viscosity, and (meth)acrylamide is preferred because they have good hydrophilicity.

Examples of component (a-7) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, vinyl acetate, etc.

Examples of component (a-8) include (meth)acrylonitrile.

The substances exemplified as monomers constituting the polymer of component (A) and known monomers constituting the polymer of component (A) can be used alone or in combination of two or more kinds.

The (A) component can be obtained by a conventional method. For example, one or more of the above monomers are placed in a container, stirred, and then subjected to a radical polymerization reaction at 50 to 100°C for 30 minutes to 10 hours. Before stirring, before the reaction, or after the reaction, one or more selected from the group consisting of a solvent, a polymerization initiator, an acidic substance, and a basic substance may be added as appropriate. Examples of the solvent include those described in detail below. An example of a preferred solvent is a solvent with a chain transfer effect such as isopropanol, which allows viscosity adjustment, etc. Examples of the polymerization initiator include persulfate initiators (e.g., ammonium persulfate, potassium persulfate, etc.), azo initiators (e.g., 2,2-azobis-(2-amidinopropane) dihydrochloride, etc.), hydrogen peroxide, ascorbic acid, etc. Examples of the basic substance include an amine compound, an alkali metal hydroxide, an alkaline earth metal hydroxide, a basic amino acid, ammonia, etc. Examples of amine compounds include triethanolamine, diethanolamine, monoethanolamine, ethylamine, butylamine, and benzylamine. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide. Examples of basic amino acids include arginine.

Component (A) may be a commercially available product. Examples of such products include polyacrylic acid (product name "AQUALIC HL", manufactured by Nippon Shokubai Co., Ltd.) (product names "ARON A-10H", "JURYMER AC-10LHPK", "JURYMER AC-10SHP", manufactured by Toagosei Co., Ltd.), sodium polyacrylate (product names "AQUALIC DL", "AQUALIC IH", "AQUALIC FH", "AQUALIC MH", manufactured by Nippon Shokubai Co., Ltd.) (product names "ARON A-20L", "ARON A-7100", manufactured by Toagosei Co., Ltd.) (product name "Sodium Polyacrylate", manufactured by Hayashi Pure Chemical Industries, Ltd.), and ammonium polyacrylate (product name "AQUALIC DL"). Examples include "Aron A-30" manufactured by Toagosei Co., Ltd.), acrylic acid/sodium acrylate copolymer (product names "Viscomate NP-800", "Viscomate NP-700", "Viscomate NP-600" manufactured by Showa Denko K.K.), acrylic acid/maleic acid copolymer salt (product name "Aqualic TL" manufactured by Nippon Shokubai Co., Ltd.), acrylic acid/sulfonic acid monomer copolymer salt (product name "Aqualic GL" manufactured by Nippon Shokubai Co., Ltd.), carboxylic acid copolymer (product names "Aron A-7185", "Aron A-7195", "Aron A-7075" manufactured by Toagosei Co., Ltd.), etc.

The substances exemplified as the component (A) and the substances known as the component (A) can be used alone or in combination of two or more kinds. The component (A) is preferably
(α) a polymer of component (a-1),
(β) a copolymer of the component (a-1) and an anionic monomer other than the component (a-1);
(γ) a copolymer of the (a-1) component and a nonionic monomer, and (δ) a copolymer of the (a-1) component, an anionic monomer other than the (a-1) component, and a nonionic monomer.
The anionic monomer other than the component (a-1) is preferably the component (a-2).
The nonionic monomer is preferably the component (a-6).

The upper limit of the number of radically polymerizable functional groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups, hydroxyl groups, and amide groups possessed by the monomers constituting the polymer of component (A) is 6, 5, 4, 3, 2, etc., respectively, and the lower limit is 5, 4, 3, 2, etc., respectively. In one embodiment, the number of radically polymerizable functional groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups, hydroxyl groups, and amide groups possessed by the monomers constituting the polymer of component (A) is preferably about 1 to 6, respectively.

The upper limit of the molecular weight of the monomer constituting the polymer of component (A) is 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, etc., and the lower limit is 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, etc. In one embodiment, the molecular weight of the monomer constituting the polymer of component (A) is preferably about 25 to 1,000. In this disclosure, "molecular weight" is a numerical value calculated from the atomic weights of the atoms constituting the molecule.

Examples of the upper limit of the pH of component (A) at a solids concentration of 1% are 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and examples of the lower limit are 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1. In one embodiment, the pH of component (A) at a solids concentration of 1% is preferably about 1 to 12.

Examples of the upper limit of the solids concentration (%) of component (A) are 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, etc., and examples of the lower limit are 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 1, 0.5, 0.1, etc. In one embodiment, the solids concentration (%) of component (A) is preferably about 0.1 to 100.

When the solids concentration of component (A) is 15%, the upper limit of viscosity (mPa·s/25°C) is 150,000, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 500, 1 Examples of the viscosity are 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 500, 100, 50, 40, 30, 20, and 10. In one embodiment, the viscosity (mPa·s/25°C) when the solid content concentration of the (A) component is 15% is preferably about 10 to 150,000. The viscosity is a value when the solid content concentration is 15% by diluting with water, etc. An example of a method for measuring viscosity is a method using a viscometer as described in JIS K 7117-1:1999.

When component (a-1) and a monomer other than component (a-1) are used as monomers constituting the polymer of component (A), the upper limit of the molar ratio [(component (a-1))/(monomer other than component (a-1)] is 100/0, 99.9/0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/20, 79/21, 75/25, 70/30, 69/31, 65/35, 60/40, 55/45, 50/50, 49/51, 45/55, 40/60, 35/65 , 30/70, 29/71, 25/75, 20/80, 15/85, 10/90, etc. are examples, and the lower limit is 99.9/0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/20, 79/21, 75/25, 70/30, 69/31, 65/35, 60/40, 55/45, 50/50, 49/51, 45/55, 40/60, 35/65, 30/70, 29/71, 25/75, 20/80, 15/85, 10/90, 5/95, etc. are examples. In one embodiment, the molar ratio of the (a-1) component to the monomer other than the (a-1) component [((a-1) component)/(monomer other than the (a-1) component)] is preferably about 5/95 to 100/0.

When anionic monomers and nonionic monomers are used as monomers constituting the polymer of component (A), the upper limit of the molar ratio [(anionic monomer)/(nonionic monomer)] is 100/0, 99.9/0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/20, 79/21, 75/25, 70/30, 69/31, 65/35, 60/40, 55/45, 50/50, 49/51, 45/55, 40/60, 35/65, 30 Examples of the lower limit include 99.9/0.1, 99.5/0.5, 99/1, 95/5, 90/10, 85/15, 80/20, 79/21, 75/25, 70/30, 69/31, 65/35, 60/40, 55/45, 50/50, 49/51, 45/55, 40/60, 35/65, 30/70, 29/71, 25/75, 20/80, 15/85, 10/90, and 5/95. In one embodiment, the molar ratio of the anionic monomer to the nonionic monomer [(anionic monomer)/(nonionic monomer)] is preferably about 5/95 to 100/0.

The molar ratio of component (a-1), which is a monomer constituting the polymer of component (A), to the anionic monomer other than component (a-1), and the nonionic monomer [component (a-1)/anionic monomer other than component (a-1)/nonionic monomer] is preferably 29-100/0-71/0-71, more preferably 49-100/0-51/0-51, even more preferably 69-100/0-31/0-31, and particularly preferably 75-100/0-25/0-25.

When the total mass of the (A) component and the (B) component is taken as 100% by mass, the upper limit of the content of the (A) component (solid content equivalent) is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10% by mass, etc., and the lower limit is 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc. In one embodiment, when the total mass of the (A) component and the (B) component is taken as 100% by mass, the content of the (A) component (solid content equivalent) is preferably about 5 to 95% by mass.

<Component (B)>
Component (B) is hydroxyethyl cellulose. If carboxymethyl cellulose and/or a salt thereof is used as an alternative to component (B), it is not preferable because after a water droplet placed on the coating of the hydrophilic water-slipping treatment agent of the present disclosure starts to slide, a water mark will remain from the position where the droplet started to slide.

Component (B) may be a commercially available product. The products in question include hydroxyethyl cellulose (product name "SANHEC", manufactured by Sansho Co., Ltd.) (product name "Natrosol (registered trademark) HEC", manufactured by Ashland Inc.) (product names "HEC Daicel SP200", "HEC Daicel SP400", "HEC Daicel SP500", "HEC Daicel SP550", "HEC Daicel SP600", "HEC Daicel SP850", "HEC Daicel SP900", "HEC Daicel SE400", "HEC Daicel SE550", "HEC Daicel SE600", "HEC Daicel SE850", "HEC Daicel SE900", and "HEC Daicel EE820", manufactured by Daicel Miraize Co., Ltd.) (product names "HEC AL-15", "HEC AL-15F", "HEC AG-15F", "HEC AH-15F", "HEC Examples include "HEC AV-15F", "HEC AW-15F", "HEC AX-15", "HEC SW-25F", "HEC SZ-25F", "HEC CF-G", "HEC CF-V", "HEC CF-W", "HEC CF-X", and "HEC CF-Y" (manufactured by Sumitomo Seika Chemicals Co., Ltd.).

The upper limit of the viscosity (mPa·s/25°C) of component (B) is 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 800, 600, 500, 400, 300, 200, 100, 50, 25 Examples of the lower limit are 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,000, 800, 600, 500, 400, 300, 200, 100, 50, 25, 10, 5, 3, and 1. In one embodiment, the viscosity (mPa·s/25° C.) of the component (B) is preferably about 1 to 100,000, more preferably 1 to 6,000, even more preferably 1 to 600, and particularly preferably 1 to 400. The viscosity is the value when diluted with water to a solids concentration of 2%. The measurement method can be the same as that for component (A). The lower the viscosity of component (B), the better the sliding angle, which is preferable. In this disclosure, "good sliding angle" refers to the fact that water droplets begin to slide even when the angle of the laminate relative to the ground is low.

Examples of the upper limit of the pH of component (B) at a solids concentration of 1% are 12, 11, 10, 9, 8, 7.6, 7.4, 7.2, 7.0, 6.8, 6.6, 6.4, 6.2, 6.0, 5, 4, 3, 2, etc., and examples of the lower limit are 11, 10, 9, 8, 7.6, 7.4, 7.2, 7.0, 6.8, 6.6, 6.4, 6.2, 6.0, 5, 4, 3, 2, 1. In one embodiment, the pH of component (B) at a solids concentration of 1% is preferably about 1 to 12.

The upper limit of the modification rate of component (B) (the proportion of hydroxyl groups in the entire cellulose that are modified by the substituent) is 100, 90, 80, 70, 60, 50, 40, 30, 20, 10%, etc., and the lower limit is 90, 80, 70, 60, 50, 40, 30, 20, 10, 5%, etc. In one embodiment, the modification rate of component (B) is preferably about 5 to 100%. The modification rate can be calculated from the elemental ratios of carbon, hydrogen, and oxygen obtained by elemental analysis. Examples of the agent and modification method used for modification include various known ones.

The upper limit of the mass ratio of the solid contents of the (A) component and the (B) component (solid content equivalent) [(A) component/(B) component] is 95/5, 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/8 Examples of the lower limit are 90/10, 85/15, 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/65, 30/70, 25/75, 20/80, 15/85, 10/90, and 5/95. In one embodiment, the mass ratio (solid content equivalent) of the solid contents of the (A) component and the (B) component [(A) component/(B) component] is preferably about 5/95 to 95/5, more preferably 10/90 to 90/10, even more preferably 20/80 to 80/20, and particularly preferably 25/75 to 75/25.

When the total mass of the (A) component and the (B) component is taken as 100% by mass, the upper limit of the content of the (B) component (solid content equivalent) is 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10% by mass, and the lower limit is 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5% by mass, etc. In one embodiment, when the total mass of the (A) component and the (B) component is taken as 100% by mass, the content of the (B) component (solid content equivalent) is preferably about 5 to 95% by mass.

<Other agents that can be added>
The hydrophilic water-slipping treatment agent of the present disclosure may further contain various additives other than those exemplified above, such as crosslinking agents, antibacterial agents, surfactants, preservatives, rust inhibitors, viscosity adjusters, pH adjusters, pigments, dyes, lubricants, leveling agents, catalysts, defoamers, photosensitizers (amines, quinones, etc.), organic particles, etc., if necessary. By not including organic particles such as polyamide particles in the hydrophilic water-slipping treatment agent of the present disclosure, the dispersibility and the like are improved, and the smoothness of the coating film formed is improved, and water-slipping properties are improved, so it is preferable not to include such particles.

Examples of the crosslinking agent of the present disclosure include crosslinking agents having an epoxy group, crosslinking agents having a carbodiimide, crosslinking agents having an oxazoline group, crosslinking agents having a cyclocarbonate, crosslinking agents having a hydroxyl group, crosslinking agents having an isocyanate group, crosslinking agents having a carboxyl group, crosslinking agents having an acid anhydride group, amino resins, phenolic resins, amines, organic peroxides, melamine resins, silane coupling agents, and organic metals. By incorporating a crosslinking agent into the hydrophilic water-smoothing treatment agent of the present disclosure, the laminate having the coating of the hydrophilic water-smoothing treatment agent is preferably further excellent in anti-fogging properties and water resistance. The substances exemplified as crosslinking agents and known crosslinking agents can be used alone or in combination of two or more types.

Examples of crosslinking agents having an epoxy group include phenol novolac type epoxides, cresol novolac type epoxides, bisphenol A type epoxides, bisphenol F type epoxides, bisphenol S type epoxides, hydrogenated bisphenol A type epoxides, hydrogenated bisphenol F type epoxides, stilbene type epoxides, triazine skeleton-containing epoxides, fluorene skeleton-containing epoxides, linear aliphatic epoxides, alicyclic epoxides, glycidylamine type epoxides, triphenolmethane type epoxides, alkyl-modified triphenolmethane type epoxides, biphenyl type epoxides, dicyclopentadiene skeleton-containing epoxides, naphthalene skeleton-containing epoxides, aryl alkylene type epoxides, tetraglycidyl xylylenediamine, dimer acid modified products of the above epoxides, dimer acid diglycidyl esters, etc.

Examples of crosslinking agents containing carbodiimide include 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 1,3-diisopropylcarbodiimide, and bis(2,6-diisopropylphenyl)carbodiimide.

Examples of crosslinking agents having an oxazoline group include polymers of 2-isopropenyl-2-oxazoline, polymers of 2-vinyl-2-oxazoline, and the product name "Epocross" (Nippon Shokubai Co., Ltd.).

Examples of crosslinking agents having hydroxyl groups include polyether polyol, polybutadiene polyol, polycaprolactone polyol, and tris(2-hydroxyethyl)isocyanurate.

Examples of crosslinking agents having an isocyanate group include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and isocyanate ethyl methacrylate. As a crosslinking agent having an isocyanate group, an adduct, polymer, or blocked product of the above crosslinking agents having an isocyanate group may also be used.

Examples of crosslinking agents having a carboxy group include ester resins having a carboxy group and aliphatic dicarboxylic acids (e.g., dodecanedioic acid, etc.).

Examples of crosslinking agents having an acid anhydride group include phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, maleic anhydride-styrene copolymer, etc.

An amino resin is a resin obtained by addition condensation of an amino compound (e.g., melamine, benzoguanamine, urea, etc.) with formaldehyde or alcohol. Examples of amino resins include melamine resin, benzoguanamine resin, tetraalkoxymethylglycoluril, urea resin, etc. Examples of melamine resins include fully alkylated melamine resin, partially alkylated melamine resin, etc.

Examples of phenolic resins include novolac-type phenolic resins and resol-type phenolic resins. Examples of novolac-type phenolic resins include products with the names Sandbond 4860SK, Sandbond 4740SK, and Sandbond 4650 (Lignite Co., Ltd.). Examples of resol-type phenolic resins include products with the names Sandbond H3-PC, Sandbond LT-H, and Sandbond LT-15 (Lignite Co., Ltd.).

Examples of amines include polymethylenediamine, diethylenetriamine, bishexamethylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, polyetherdiamine, diaminocyclohexane, diaminodiphenylmethane, diaminodiphenylsulfone, bis(acetoacetyl)-o-toluidine, phenylenediamine, methylpiperazine, morpholine, triethanolamine, and dialkylaminoethanol.

Examples of organic peroxides include di(4-methylbenzoyl) peroxide, dibenzoyl peroxide, di(t-butylperoxy)cyclohexane, butylperoxy-2-ethylhexyl monocarbonate, butyl-4,4-di(t-butylperoxy)valerate, dicumyl peroxide, and di(t-hexylperoxy)cyclohexane.

Examples of organometallic compounds include organotitanium compounds, organozirconium compounds, and organoaluminum compounds. Examples of organotitanium compounds include titanium alkoxides and titanium chelates. Examples of organozirconium compounds include zirconium alkoxides and zirconium chelates. Examples of organoaluminum compounds include aluminum alkoxides and aluminum chelates.

Other examples of crosslinking agents include oxazolidine and hydroxypropyl carbamate.

Antibacterial agents include imidazole antibacterial agents (e.g., 2-(4-thiazolyl)benzimidazole, 2-benzimidazolecarbamic acid methyl, etc.), thiazole antibacterial agents (e.g., 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, etc.), iodine antibacterial agents (e.g., 3-iodo-2-propargylbutylcarbamic acid, 4-chlorophenyl-3-iodopropargylformal, etc.), nitrile antibacterial agents (e.g., 2,3,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluoro isophthalonitrile, etc.), phenol-based antibacterial agents (e.g., p-chloro-m-cresol, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), haloalkylthio-based antibacterial agents (e.g., N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl-N'-(dichlorofluoromethylthio)-N'-phenylsulfamide, N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide, etc.), pyridine-based antibacterial agents (e.g., sodium 2-pyridinethiol-1-oxide, sodium 2-pyridinethiol-1 -zinc oxide, etc.), triazine antibacterial agents (e.g., hexahydro-1,3,5-tris(2-hydroxyethyl)-S-triazine, hexahydro-1,3,5-triethyl-S-triazine, etc.), bromine antibacterial agents (e.g., 2-bromo-2-nitro-1,3-propanediol, 1,2-dibromo-2,4-dicyanobutane, etc.), inorganic antibacterial agents (e.g., silver zeolite, zinc zeolite, barium metaborate, copper borate, zinc borate, zeolite (aluminosilicate), etc.), halodiallylurea antibacterial agents (e.g., triclocarban, etc.), Examples of the antibacterial agents include guanidine-based antibacterial agents (e.g., chlorohexadine gluconate, polyhexamethylene biguanidine hydrochloride, etc.), dithiocarbamate-based antibacterial agents (e.g., bis(dimethylthiocarbamoyl)disulfide, etc.), fatty acid ester-based antibacterial agents (e.g., propyl glycol mono fatty acid ester, glycerin fatty acid ester, etc.), polymer-coordinated metal-based antibacterial agents (e.g., cellulose copper, copper cross-linked acrylonitrile-acrylic acid copolymer, etc.), and other antibacterial agents (e.g., 10,10'-oxybisphenoxyarsine, 8-oxyquinoline copper, etc.). The substances exemplified as antibacterial agents and known antibacterial agents can be used alone or in combination of two or more types.

The hydrophilic water-slipping treatment agent of the present disclosure may contain a surfactant to the extent that the hydrophilic water-slipping property is not decreased and the agent cannot be used as a hydrophilic water-slipping treatment agent. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Examples of nonionic surfactants include aliphatic alcohol alkylene oxide adducts, (poly)oxyalkylene higher fatty acid esters, polyhydric alcohol fatty acid esters, (poly)oxyalkylene polyhydric alcohol higher fatty acid esters, fatty acid alkanolamides, (poly)oxyalkylene alkylphenyl ethers, (poly)oxyalkylene alkylamino ethers, and alkylamine oxides. Examples of anionic surfactants include hydrocarbon ether carboxylic acids or their salts, hydrocarbon sulfate ester salts, hydrocarbon sulfonates, hydrocarbon phosphate ester salts, fatty acid salts, and acylated amino acid salts. Examples of cationic surfactants include amine salt types, etc. Examples of amphoteric surfactants include betaine-type amphoteric surfactants and amino acid-type amphoteric surfactants.

Examples of pH adjusters include acidic substances (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.) and basic substances (sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc.).

Examples of rust inhibitors include zirconium compounds, vanadium compounds, titanium compounds, niobium compounds, phosphorus compounds, cerium compounds, and chromium compounds.

The hydrophilic water lubricating agent of the present disclosure may be used by blending a solvent to adjust the viscosity as necessary. Examples of the solvent include water and organic solvents. The organic solvent may be any of various known solvents. Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, amide solvents, etc.

Examples of ketone solvents include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.

Examples of aromatic solvents include toluene and xylene.

Examples of alcohol solvents include methanol, ethanol, n-propanol, isopropanol, butanol, etc.

Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, etc.

Examples of glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

Examples of ester solvents include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

Examples of petroleum-based solvents include T-SOL 100 (manufactured by ENEOS Corporation) and T-SOL 150 (manufactured by ENEOS Corporation).

Examples of haloalkane solvents include chloroform.

Examples of amide solvents include dimethylformamide.

The substances exemplified as organic solvents and known organic solvents can be used alone or in combination of two or more types.

The upper limit of the solvent content when the total mass of the (A) component and the (B) component is 100 mass % is 20,000, 15,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 500, 400 , 100, 50, 25% by mass, etc. are exemplified, and the lower limit is 15,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,900, 1,800, 1,700, 1,600, 1,500, 1,400, 1,300, 1,200, 1,100, 1,000, 500, 400, 100, 50, 25, 10% by mass, etc. In one embodiment, the content of the solvent relative to 100% by mass, where the total mass of the (A) component and the (B) component is 100% by mass, is preferably about 10 to 20,000% by mass, and more preferably about 400 to 10,000% by mass.

<Hydrophilic Slippery Treatment Agent>
The hydrophilic water-slipping treatment agent of the present disclosure can be obtained by mixing the component (A) and the component (B), and the additives as necessary (basic substances, acidic substances, antibacterial agents, solvents, crosslinking agents, etc.). The hydrophilic water-slipping treatment agent of the present disclosure can be prepared appropriately without any particular limitations on the order of blending. For example, the component (A) and the component (B), and the additives as necessary, may be mixed at room temperature and stirred for 0.1 to 24 hours, or the additives mixed in advance as necessary and the component (A) may be mixed with a liquid obtained by stirring the additives mixed in advance as necessary and the component (B) at room temperature for 0.5 to 24 hours, and the liquid obtained by stirring the additives mixed in advance as necessary and the component (B) at room temperature for 0.5 to 24 hours may be mixed with the component (A). Alternatively, the additives mixed in advance as necessary and the liquid obtained by stirring the component (A) and the component (B) at room temperature for 0.5 to 24 hours may be mixed with the additives mixed as necessary.

The upper limit of the pH of the aqueous solution in which the combined solids concentration of components (A) and (B) is 1% is 5.0, 4.8, 4.6, 4.4, 4.2, 4.0, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.6, 2.4, 2.2, etc., and the lower limit is 4.8, 4.6, 4.4, 4.2, 4.0, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.6, 2.4, 2.2, 2.0, etc. The pH of the aqueous solution in which the combined solids concentration of components (A) and (B) is 1% is 2.0 to 5.0. If the pH is less than 2.0, the substrate may be corroded by the action of the hydrophilic water-slipping treatment agent, which is not preferable. The pH is measured after dissolving the hydrophilic lubricant in water or the like so that the combined solids concentration of components (A) and (B) is 1%.

<Laminate>
The present disclosure provides a coating of a hydrophilic water-slipping treatment agent. The present disclosure also provides a laminate having a coating of a hydrophilic water-slipping treatment agent on at least one surface of a substrate. The present disclosure also provides a method for forming a coating of a hydrophilic water-slipping treatment agent, the method including a step of applying the hydrophilic water-slipping treatment agent to the surface of the substrate.

Examples of substrates to which the hydrophilic water-slipping treatment agent of the present disclosure is applied include glass substrates, metal substrates, and plastic substrates. Examples of metal substrates include gold, silver, copper, tin, nickel, aluminum, titanium, molybdenum, zinc, cobalt, chromium iron-nickel-cobalt alloy, tungsten, copper-tungsten, invar, galvalume steel sheet (registered trademark), and ZAM steel sheet. Examples of plastic substrates include thermoplastic plastic substrates and thermosetting plastic substrates. Examples of thermoplastic plastic substrates include general-purpose plastic substrates and engineering plastic substrates. Examples of general-purpose plastic substrates include olefin-based, polyester-based, acrylic-based, vinyl-based, and polystyrene-based substrates. Examples of olefin-based substrates include polyethylene, polypropylene, and norbornene. Examples of polyester-based substrates include polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Examples of acrylic-based substrates include polymethyl methacrylate (PMMA). Examples of vinyl-based materials include polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol. Examples of polystyrene-based materials include polystyrene (PS) resin, styrene-acrylonitrile (AS) resin, and styrene-butadiene-acrylonitrile (ABS) resin. Examples of engineering plastic substrates include general-purpose engineering plastics and super engineering plastics. Examples of general-purpose engineering plastics include polycarbonate and polyamide (nylon). Examples of super engineering plastics include polyether ether ketone (PEEK). Examples of thermosetting plastic substrates include polyimide, epoxy resin, and melamine resin. Examples of other plastic substrates include triacetyl cellulose resin. The substrate may be subjected to surface treatment (corona discharge, metal deposition, plating, etc.), rust prevention treatment, and chemical conversion treatment. Examples of rust prevention treatment include mirror finishing. Examples of surface treatment include plating treatment using a plating solution containing Ni, Zn, Sn, etc., treatment with zirconium phosphate, and chromate treatment. Examples of chromate treatment include the use of chromate phosphate and chromate chromate. Other layers (e.g., an easy-adhesion layer, an anchor layer, etc.) may be provided between the film formed by the hydrophilic water-smoothing treatment agent of the present disclosure provided on one or both sides of the substrate. The substrate is preferably a metal substrate or a plastic substrate, more preferably aluminum, galvalume steel plate, ZAM steel plate, or a thermoplastic plastic, even more preferably aluminum, galvalume steel plate, ZAM steel plate, or a general-purpose plastic, and particularly preferably aluminum, galvalume steel plate, ZAM steel plate, or a polyester-based substrate. The substrate to which the hydrophilic water-smoothing treatment agent of the present disclosure is applied is preferably a metal substrate, more preferably aluminum, since the film of the hydrophilic water-smoothing treatment agent of the present disclosure is easily adhered to the substrate. The thickness of the substrate is not particularly limited, and is usually about 1 to 2 mm.

Examples of methods for applying the hydrophilic water-slipping treatment agent of the present disclosure to a substrate include roll coater coating, reverse roll coater coating, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, etc. The amount of coating is not particularly limited, but is usually in the range of 0.1 to 10.0 g/m2, preferably 0.5 to 5.0 g/ ^m2 , and more preferably 0.5 to 2 g/m2, so that the mass after drying is 0.1 to 10.0 g/m2, preferably 0.5 to 5.0 g/ ^m2 , and more preferably 0.5 to 2 g/ ^m2 . The thickness of the coating of the hydrophilic water-slipping treatment agent of the present disclosure is about 0.1 to 10 μm.

After the hydrophilic water-slipping treatment agent is applied to the surface of the substrate, a drying step may be performed as necessary. The drying step of the present disclosure is sufficient if it dries the hydrophilic water-slipping treatment agent applied to the substrate. An example of the drying step of the present disclosure is drying at about 60 to 350°C for about 10 seconds to 60 minutes. An example of the drying step of the present disclosure is preferably drying at 100 to 250°C for about 10 seconds to 5 minutes.

The coating of the hydrophilic water-slipping treatment agent disclosed herein adheres easily to metals and has excellent hydrophilic water-slip properties, so it can be used, for example, on aluminum fins for air conditioning and heating, and on car bodies.

In addition, the hydrophilic water-slipping treatment agent disclosed herein may be used for a variety of other purposes that can demonstrate its effects.

The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and percentages are by weight unless otherwise specified.

Synthesis Example 1: Synthesis of Component (A-1)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 186.8 parts of an 80% aqueous acrylic acid solution (solid content: 149.4 parts) and 776.6 parts of ion-exchanged water, and oxygen was removed from the reaction system through nitrogen gas. The temperature inside the system was set to 60°C, and 0.54 parts of ammonium persulfate was dissolved in 10.6 parts of ion-exchanged water as a polymerization initiator and added while stirring. The temperature was raised to 90°C, and the mixture was kept warm for 2 hours. After the polymerization was completed, 25.5 parts of ion-exchanged water was added to obtain an (A-1) component having a solid content concentration of 15% by mass and a viscosity (25°C) of 40,000 mPa·s. The monomer composition and physical properties of the obtained (A-1) component are shown in Table 1. The viscosity was measured at 25°C using a B-type viscometer (product name "VISCOMETER TVB-10", manufactured by Toki Sangyo Co., Ltd.) using No. Measurements were performed using a 4 rotor at a rotation speed of 6 rpm.

Synthesis Example 2: Synthesis of Component (A-2)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and two dropping funnels was charged with 50.6 parts of ion-exchanged water, and oxygen in the reaction system was removed by passing nitrogen gas through it, and then the reaction system was heated to 90°C. 249.0 parts of 80% acrylic acid aqueous solution (solid content: 199.2 parts), 2.64 parts of sodium methallylsulfonate, 0.129 parts of N,N'-methylenebisacrylamide, and 325.3 parts of ion-exchanged water were charged into one dropping funnel. 0.283 parts of ammonium persulfate and 180.0 parts of ion-exchanged water were charged into the other dropping funnel. Next, the monomer and catalyst were dropped into the system from both dropping funnels over about 3 hours. After the dropping was completed, 0.20 parts of ammonium persulfate was dissolved in 10.0 parts of ion-exchanged water and added. After keeping the mixture warm for 1 hour, 194.2 parts of ion-exchanged water was added to obtain an (A-2) component having a solid content of 20% by mass and a viscosity (25°C) of 6,000 mPa·s. The monomer composition and physical properties of the obtained (A-2) component are shown in Table 1. The viscosity was measured in the same manner as in Synthesis Example 1, except that the rotor was changed to a No. 3 rotor and the rotation speed was changed to 12 rpm.

Synthesis Example 3: Synthesis of component (A-3)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and two dropping funnels was charged with 277.1 parts of ion-exchanged water, and the oxygen in the reaction system was removed through nitrogen gas, and then the reaction system was heated to 90°C. 367.7 parts of 80% aqueous acrylic acid solution (solid content: 294.2 parts), 5.86 parts of sodium methallylsulfonate, and 226.5 parts of ion-exchanged water were charged into one dropping funnel. In addition, 0.60 parts of ammonium persulfate and 90 parts of ion-exchanged water were charged into the other dropping funnel. Next, the monomer and catalyst were dropped into the system from both dropping funnels over about 3 hours. After the end of the dropping, 0.30 parts of ammonium persulfate was dissolved in 10 parts of ion-exchanged water and added. After keeping warm for 1 hour, 25.0 parts of ion-exchanged water was added to obtain an (A-3) component having a solid content concentration of 30% by mass and a viscosity (25°C) of 3,000 mPa·s. The monomer composition and physical properties of the obtained component (A-3) are shown in Table 1. The viscosity was measured in the same manner as in Synthesis Example 1, except that the rotor was changed to a No. 3 rotor and the rotation speed was changed to 12 rpm.

<Synthesis Examples 4 to 9 and Comparative Synthesis Example 1: Synthesis of Components (A-4) to (A-9) and Component (A-C1)>
Synthesis Examples 4 to 9 and Comparative Synthesis Example 1 were carried out in the same manner as Synthesis Example 2, except that the compositions were changed to those shown in Table 1, to obtain solutions of components (A-4) to (A-9) and solutions of components (A-C1). The concentrations of the obtained polymers, components (A-4) to (A-9) and components (A-C1), and their viscosities (mPa·s) at 25°C are summarized in Table 1. The viscosities of components (A-4) to (A-5), components (A-7) to (A-9), and components (A-C1) were measured in the same manner as Synthesis Example 1, except that the rotor was changed to a No. 3 rotor and the rotation speed was changed to 12 rpm. The viscosity of component (A-6) was measured in the same manner as Synthesis Example 1, except that the rotor was changed to a No. 2 rotor and the rotation speed was changed to 30 rpm.

<Synthesis Example 10: Synthesis of component (A-10)>
Synthesis Example 10 was carried out in the same manner as Synthesis Example 1, except that the composition was changed to that shown in Table 1, to obtain a solution of component (A-10). The concentration and viscosity (mPa·s) at 25° C. of the obtained polymer, component (A-10), are summarized in Table 1. The viscosity of component (A-10) was measured in the same manner as Synthesis Example 1, except that the rotor was changed to a No. 2 rotor and the rotation speed was changed to 30 rpm.

The terms in Table 1 have the following meanings:
AA: Acrylic acid (product name "80% acrylic acid", manufactured by Osaka Organic Chemical Industry Co., Ltd.)
IA: Itaconic acid (product name: "Purified Itaconic Acid", manufactured by Fuso Chemical Co., Ltd.)
MAA: Methacrylic acid (product name "Methacrylic acid 80", manufactured by Mitsubishi Chemical Corporation)
SMAS: Sodium methallylsulfonate (product name: "Sodium methallylsulfonate", purchased from Maruzen Yuka Shoji Co., Ltd.)
AM: Acrylamide (product name: "Acrylamide (50% aqueous solution)", manufactured by Mitsubishi Chemical Corporation)
MBAA: N,N'-methylenebisacrylamide (product name: "N,N'-methylenebisacrylamide", manufactured by MCC Unitech Co., Ltd.)

Example 1: Preparation of hydrophilic lubricating agent (1)
In Example 1, 50 parts of component (A-1) calculated as solid content and 50 parts of hydroxyethyl cellulose (product name "HEC Daicel SP200, manufactured by Daicel Miraize Co., Ltd.) calculated as solid content were mixed and diluted with ion exchanged water to a solid content of 5%, to prepare a hydrophilic water-slipping treatment agent (1).

<Examples 2 to 32, 34 to 40 and Comparative Examples 1 to 37: Preparation of hydrophilic slipping treatment agents (2) to (32), (34) to (40), and (C1) to (C37)>
Examples 2 to 32, 34 to 40 and Comparative Examples 1 to 37 were carried out in the same manner as Example 1, except that the compositions were changed to those shown in Tables 2 to 5, to obtain hydrophilic slipping treatment agents (2) to (32), (34) to (40) and (C1) to (C37). Note that in the examples and comparative examples in which a pH adjuster was added, the pH adjuster was added after the addition of component (B).

Example 33: Preparation of hydrophilic lubricating agent (33)
In Example 33, 50 parts of component (A-1) calculated as solid content and 50 parts of hydroxyethyl cellulose (product name "HEC Daicel SP600, manufactured by Daicel Miraize Co., Ltd.) calculated as solid content were mixed, and then potassium hydroxide (product name "Liquid Caustic Potash", manufactured by AGC Co., Ltd.) was added and the mixture was diluted with ion exchanged water to a solid content of 1%, to prepare a hydrophilic water slipping treatment agent (33).

<Evaluation Example 1: Preparation of Laminate (1)>
The hydrophilic water-slipping treatment agent (1) was applied to an aluminum substrate (thickness 100 μm) treated with chromate phosphate using a bar coater No. 14 (film thickness 1 μm after drying), and dried at 200° C. for 1 minute to obtain a laminate (1).

<Evaluation Examples 2 to 32, 34 to 40 and Comparative Evaluation Examples 1 to 37: Preparation of Laminates (2) to (32), (34) to (40), and (C1) to (C37)>
Evaluation Examples 2 to 32, 34 to 40 and Comparative Evaluation Examples 1 to 37 were carried out in the same manner as Evaluation Example 1, except that the hydrophilic smoothing treatment agent (1) was changed to the hydrophilic smoothing treatment agents (2) to (32), (34) to (40) or (C1) to (C37), respectively, and the substrates were changed to those shown in Tables 2 to 5, to obtain laminates (2) to (32), (34) to (40) and (C1) to (C37).

<Evaluation Example 33: Preparation of laminate (33)>
The hydrophilic water-slipping treatment agent (33) was applied to an aluminum substrate (thickness 100 μm) treated with chromate phosphate using a bar coater No. 3 (film thickness 1 μm after drying), and dried at 200° C. for 1 minute to obtain a laminate (33).

<Performance evaluation (1): Fall angle test>
10 μL of ultrapure water was applied to the coating surface of the hydrophilic water-slipping treatment agent of the laminate placed horizontally to the ground. 10 seconds after the application, the laminate was tilted from 0° to 90° at a speed of 1°/sec, and the angle of the laminate with respect to the ground at the moment when the water droplet started to slide based on the end point on the receding angle side was measured using a measuring device (product name "Contact angle meter LSE-B100W", manufactured by NIC Co., Ltd.) and a tilt unit (product name "TBU-100", manufactured by NIC Co., Ltd.) under the conditions of zoom ring 0.3× and movement detection 5 pixels (relative movement detection). Relative movement detection is a condition in which movement detection is performed based on an image of a tilt angle of 0.5° before.
The measured falling angle was evaluated according to the following criteria.
AAA: 0° or more and less than 31° AA: 31° or more and less than 51° A: 51° or more and less than 71° B: 71° or more and less than 90° C: Non-slip

<Performance evaluation (2): Checking water marks>
In the <Performance evaluation (1): Falling angle test>, after the applied water droplet started to slide, the presence or absence of a water mark from the position where the droplet started to slide was confirmed. The confirmed results were evaluated according to the following criteria.
No: No water marks Yes: Water marks

<Performance evaluation (3): Hydrophilicity test>
1 μL of ultrapure water was applied to the coating surface of the hydrophilic water-slipping agent of the laminate placed horizontally on the ground. 10 seconds after the water was applied, the contact angle of a water droplet on the coating surface of the hydrophilic water-slipping agent of the laminate was measured using a measuring device (product name: Contact Angle Meter DM-500, manufactured by Kyowa Interface Science Co., Ltd.). The measured contact angles were evaluated according to the following criteria.
AA: 0° or more and less than 41° A: 41° or more and less than 61° B: 61° or more and less than 90°

The terms in Tables 2 to 5 have the following meanings.
In the table, the numerical values for the components indicate parts by mass.
AL: Aluminum substrate treated with chromate phosphate (thickness: 100 μm)
PET: Polyester film (product name "Cosmoshine A4100", manufactured by Toyobo Co., Ltd., thickness: 100 μm)
ZAM: ZAM steel plate (thickness 1.2 mm, manufactured by Nippon Test Panel Co., Ltd.)
GL: Galvanized steel sheet (thickness 0.5 mm, manufactured by Nippon Test Panel Co., Ltd.)
HEC Daicel SP200: Hydroxyethyl cellulose (product name "HEC Daicel SP200", manufactured by Daicel Miraize Co., Ltd., viscosity (mPa·s) at solids concentration of 2%: 10.6, pH at solids concentration of 1%: 6.2)
HEC Daicel SP400: Hydroxyethyl cellulose (product name "HEC Daicel SP400", manufactured by Daicel Miraize Co., Ltd., viscosity (mPa·s) at solids concentration of 2%: 108, pH at solids concentration of 1%: 6.6)
HEC Daicel SP500: Hydroxyethyl cellulose (product name "HEC Daicel SP500", manufactured by Daicel Miraize Co., Ltd., viscosity (mPa·s) at solids concentration of 2%: 372, pH at solids concentration of 1%: 6.4)
HEC Daicel SP600: Hydroxyethyl cellulose (product name "HEC Daicel SP600", manufactured by Daicel Miraize Co., Ltd., viscosity (mPa·s) at solids concentration of 2%: 5,310, pH at solids concentration of 1%: 6.5)
HEC AL-15: Hydroxyethyl cellulose (product name "HEC AL-15", manufactured by Sumitomo Seika Chemicals Co., Ltd., viscosity (mPa s) at solids concentration of 2%: 27, pH at solids concentration of 1%: 6.1)
HEC AL-15F: Hydroxyethyl cellulose (product name "HEC AL-15F", manufactured by Sumitomo Seika Chemicals Co., Ltd., viscosity (mPa s) at solids concentration of 2%: 27, pH at solids concentration of 1%: 5.9)
HEC AG-15F: Hydroxyethyl cellulose (product name "HEC AG-15F", manufactured by Sumitomo Seika Chemicals Co., Ltd., viscosity (mPa·s) at solids concentration of 2%: 250, pH at solids concentration of 1%: 6.0)
HEC CF-G: Hydroxyethyl cellulose (product name "HEC CF-G", manufactured by Sumitomo Seika Chemicals Co., Ltd., viscosity (mPa s) at solids concentration of 2%: 510, pH at solids concentration of 1%: 6.1)
Polyvinyl alcohol: Polyvinyl alcohol (product name "Kuraray Poval PVA-117", manufactured by Kuraray Co., Ltd.)
Polyethylene oxide: Polyethylene oxide (product name "PEO-1", manufactured by Sumitomo Seika Chemicals Co., Ltd.)
Polyglycerin: Polyglycerin (product name "PGL 20PW", manufactured by Daicel Corporation)
Sodium alginate: Sodium alginate (product name: "Sodium Alginate 80-120", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
Methylcellulose: Methylcellulose (product name: "Metolose SM-15", manufactured by Shin-Etsu Chemical Co., Ltd.)
Hydroxypropyl cellulose: Hydroxypropyl cellulose (product name: "Hydroxypropyl cellulose 6.0-10.0", Fujifilm Wako Pure Chemical Industries, Ltd.)
Hydroxypropyl methylcellulose: Hydroxypropyl methylcellulose (product name: "Metolose 60SH-03", manufactured by Shin-Etsu Chemical Co., Ltd.)
Sodium hydroxide: Sodium hydroxide (product name: Liquid caustic soda, manufactured by Nippon Soda Co., Ltd.)
Potassium hydroxide: Potassium hydroxide (product name: "Liquid Caustic Potash", manufactured by AGC, Inc.)
Ammonia: Ammonia (product name: "28% ammonia water", manufactured by Taisei Kako Co., Ltd.)
Sulfuric acid: sulfuric acid (product name: "50% sulfuric acid", manufactured by Furukawa Chemicals Co., Ltd.)
Hydrochloric acid: Hydrochloric acid (product name: "Hydrochloric Acid", Kaname Pharmaceutical Co., Ltd.)
Phosphoric acid: Phosphoric acid (product name: "Phosphoric acid (special grade)", manufactured by Kishida Chemical Co., Ltd.)
pH: pH of an aqueous solution in which the combined solids concentration of components (A) and (B) is 1%. The pH was measured at 25°C using a pH meter (product name "Desktop pH Meter F-71", manufactured by Horiba Advanced Techno Co., Ltd.) based on the pH measurement method described in JIS Z 8802:2011.

Claims (6)

A polymer (A) containing a radical polymerizable monomer having a carboxy group and/or a salt thereof (a-1) as a reaction component;
and hydroxyethyl cellulose (B),
a mass ratio of the component (A) to the component (B) [(A)/(B)] in terms of solid contents is 5/95 to 95/5;
the pH of an aqueous solution in which the combined solids concentration of components (A) and (B) is 1% is 2.0 to 5.0;
A hydrophilic, water-slipping treatment agent having a viscosity (mPa·s/25° C.) of 1 to 600 when the component (B) is diluted with water at a solids concentration of 2% . 2. The hydrophilic smoothing treatment agent according to claim 1, wherein the component (a-1) comprises at least one member selected from the group consisting of (meth)acrylic acid, salts of (meth)acrylic acid, itaconic acid, salts of itaconic acid, itaconic acid monoesters, salts of itaconic acid monoesters, and itaconic anhydride. 3. The hydrophilic smoothing treatment agent according to claim 1, wherein the component (a-1) accounts for 29 mol % or more of the monomers constituting the polymer of the component (A). 4. The hydrophilic water-slipping treatment agent according to any one of claims 1 to 3, wherein component (A) is at least one selected from the group consisting of poly(meth)acrylic acid, a copolymer of (meth)acrylic acid and (meth)acrylamide, a copolymer of (meth)acrylic acid and an anionic monomer other than (meth)acrylic acid, a copolymer of (meth)acrylic acid, (meth)acrylamide and an anionic monomer other than (meth)acrylic acid, and salts thereof. A laminate having a coating of the hydrophilic water-slipping treatment agent according to any one of claims 1 to 4 on at least one surface of a substrate. A method for forming a coating of a hydrophilic water-slipping treatment agent, comprising the step of applying the hydrophilic water-slipping treatment agent according to any one of claims 1 to 4 to a surface of a substrate.